Purified polyethenoxy alkylphenyl ethers



United States Patent i,i-is,ss4 PURIFIED POLYETHENOXY ALKYLPI'I'ENYL ETHERS Emil M. Stoltz, Joliet, 11L, assignor, by mesne assignments, to 01in Mathieson Chemical Corporation, New York, N. Y., a corporation of Virginia v I No Drawing. Application April 21, 1953, I

Serial No. 350,219

Claims. Cl. 260-613 The present invention relates generally to non-ionic compounds and mixtures of a kind made by condensing alkyl phenol with ethylene oxide, and more particularly to a chemical treatment of the reaction mass to improve the color and general utility thereof, including a lightening of its color and a modification of some physical qualities.

The class of compounds involved as the raw material for practice of the present invention is technically referred to as polyethenoxy ether of alkyl phenol. The material results from several reactions during the condensation, including ether-forming condensation between the alkyl phenol and ethylene oxide and between the resulting etheralcohols and ethylene oxide. In consequence, the reaction mass is a complex mixture commonly identified by its average molecular Weight and by the average number of ethylene oxide (or ethenoxy) units involved in a formula representing a single compound according to said average molecular weight. Such a general formula is wherein A represents an alkyl radical and n represents a numerical value not necessarily a whole number.

Compounds in which radical A is mixed octylor nonylisomers and in which n varies from 2 to 15, are wellg known commercially as dispersants and .detergentsin an aqueous medium, the water-solubility increasing with values 'of' n, and in general beginning where n equals 7. This last value is not precise because at a border line region part of the mixture may be readily soluble in water while the remainder is merely water-dis'persible. Q

The above-described materials are normally. liquid at room temperature orare solids melting below 60 C. The condensation reaction mass is dark colored. The dark coloration is a' deterrent to saleability of the liquid detergent materials and to their general" utility. The liquid detergent materials are commonly used as an ingredient in solid comminuted detergent compounds, being present with solid detergent inorganic salts which are white in color when used as clean crystals. Where the colored subject ether mass is an ingredient with such-white salts, its dark color renders'the resulting solid compound dirty in appearance which is objectionable.

The present invention aims toimprove'the utility of such dark-colored :ethermasses resulting from such condensation. w 3 7 n, V 3

It is a general' object of the invention to lighten the color thereof by chemical reaction which attacks the colored impurities, forming new lighter colored ingredients therefrom. i i f It is a particular object of the invention to subject a colored reaction mass of the subject ethers to theaction of hydrogen peroxide; l i

' Various other and ancillary objects and advantages of the present invention will'appear from the following description and explanation of the invention in connection with its preferred use to form lighter colored detergents from original condensation reaction masses. From the following illustrative examples and explanationfit will destroy the attendant fluorescent qualities.

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be appreciated that the present invention in its broadest aspect is not limited to and by the illustrative examples.

The condensation of alkyl phenol and ethylene oxide to form the subject ether complex is no part of the present invention, it being well-known. The basic reaction is described in U. S. No. 1,970,578 issu'ed'to Schoeller and Wittwer, wherein an organic compound having an active hydrogen atom condenses with ethylene oxide in a chain reaction. Others have specifically described the organic compound as an alkyl phenol or mixture thereof, for example, Black in U. S. No. 2,555,285 and British No. 470,181, for'producing non-ionic detergents.

The present invention is based in part upon the discovery that in'tlie 'condensations involving ethylene oxide there is a side reaction which is disadvantageous. Ethylene oxide reverts to ethylene and 'oxygen as follows:

The above reaction is a well-known equilibrium reaction by which ethylene oxide is commercially produced when it runs to the left. At the elevated temperatures of to 210 C. at which such condensations are carried out, with an alkaline catalyst, there is opportunity for this reversion to occur. The released oxygen is active to eifect an oxidation. In the condensation reaction with alkyl phenol, formation of a quinoid structure is evident by the newly-created fluorescence of the reaction mass. The fluorescence and the darkening increaseand decrease together, and by the corrective reaction of the present invention bothmay be destroyed.

The present invention is based on 'the discovery that when the fluorescent dark-colored subject ether masses are treated with hydrogen peroxide, the latter reacts with the colored ingredients without any evidence of appreciable reactionon the ether-alcohol ingredients having the benzene ring Progress of the reaction may be followed by measuring the change in light-transmittancy of the mass. By subjecting a known amount of the subject ether masses having'the, dark color to gradual additions of known amounts of hydrogen peroxide and by following the color change, the subject ether masses may be in effect evaluated for the content of colored substances, and the endpointfor their removal by hydrogen peroxide may be determined. The darker the original color, the more hydrogen peroxide is needed to remove the color and The loss of fluorescence clearly indicates that the quinoid structures have been destroyed. The situation is unusual in that the quinoid structures are seemingly formed by one type of oxidation and are then seemingly destroyed by an oxidizingagent. The observations and results described hereinabove conform to a sequence of well-known types of chemical reactions, which as applied to the present invention appear to be a plausible explanation. The following is believed to explain the reactions, but it is not to be assumed that this is the only explanation, and no intention is herein expressed to be bound by it.

=0H 0 I 3 A \l A e A (III) 'The compound I represents alkyl phenol with its benzene ring. In the presence of oxygen derived from the ethylene oxide it may form one or both of compounds II and III. structure Compounds II and III having the quinoid explain the fluorescence in the subject ether masses. When hydrogen peroxidereacts with the subject ether masses containing the colored compounds which fluoresce and which appear to be compounds II and III, new compounds are formed. In the following reaction radical 'IV represents the substituted quinoid ring of compounds II and III which adds hydrogen peroxide to form the probable radical V.

I pH na Q Q A A (V) In other words, there is glycol formation breaking at least one double bond in the quinoid ring with the result that the fluorescing quinoid structure disappears and with the result that the new glycol compound is more com patible with water.

Table I shows the change in red light-transmittancy ot I. Ether mass wherein 11:85 and A is mixed nonyl isomers I. Ether mass wherein n=11 and A is mixed nonyl isomers K. Ether mass wherein n=11 and A is mixed octyl iso mers N. Ether mass wherein n= and A is mixed octyl isomers O. Ether mass wherein n=2 1 and A is mixed octyl isomers The color value is reported'as percent transmission, its absolute value being not critical, but the change being of significance.

TABLE I Aqueous 30% Hydrogen Percent; Color Transmission! Peroxide, ml. per gm. other I .T K N O 1 100% is the transmission by water.

The dark-colored fluorescent compounds involved in the present invention result independently of the alkyl radical, and are the result of reaction involving the benzene nucleus and the oxygen'from the ethylene oxide. The corrective agent of the present invention is an aqueous solution of hydrogen peroxide, which must mix with the condensation mass to be effective. The solubility or dispersibility in water of the condensation reaction mass depends for any particular alkyl phenol upon the number of ethenoxy units in the reaction mass.

The most common and useful ones of the polyethenoxy ethers of alkyl phenol are the non-ionic detergent ones of octyl phenol and of nonyl phenol which are watersoluble. The octyl and nonyl phenols employed are the commercial mixtures. In these there are ortho, meta and para compounds of the various alkyl isomers. Paracompounds predominate, and in the case of octyl phenols the iso-octyl radical predominates.

In preparing ether masses for practice of the present invention the various methods known to the art may be employed. These vary in catalyst, temperature and other factors. The ones identified hereinabove have been prepared by passing ethylene oxide into the alkyl phenol at a temperature in the range from to 200 C. in the presence of an alkaline catalyst. The following examples illustrate the preparation of the five ether masses of Table I.

Example 1.Ether Mass N Example 2.Ether Mass K The conditions of Example 1 were maintained for a longer time until 235 grams of ethylene oxide was absorbed.

Example 3.Ether Mass 0 The conditions of Example 1 were maintained for a longer time until 427 grams of ethylene oxide were absorbed. The resulting ether mass solidified on cooling to room temperature.

Example 4.-Ether Mass 1 As in Example 1, 100 grams of commercial nonyl phenol isomers were treated to absorb grams of ethylene oxide.

Example 5.--Ether Mass J The conditions of Example 1 were maintained except for using 218 grams of ethylene oxide in the condensation. The product was semi-solid at room temperature.

In any of the foregoingexamples the catalyst may be changed to sodium acetate, or sodium hydroxide, or potassium'hydroxide, or sodium carbonate. The following example illustrates such a change.

Example 6 In a four-liter stainless steel autoclave 395 grams of commercial nonylphenol and 2.2 grams of sodium hydroxide is subjected to condensation at 160 to C. with ethylene oxide until 870 grams of the latter are absorbed. The ether mass has an average of 11 ethenoxy units, is liquid, is colored brown, and is fluorescent. Upon treatment with hydrogen peroxide it is changed to a clear amber color and is non-fluorescent.

Example 7 The procedure of Example 1 is carried out, butwith a change of the temperature to 210 C. before the ethylene oxide is introduced.

The products of the present invention are those which are compatible with aqueous hydrogen peroxide, and the term water-dispersible is used herein to comprehend water-soluble. Although the preferred com pounds are those useful in or as detergents, the utility of the products is not set forth as a limitation of the invention.

Accordingly, a wide variety of polyethenoxy alkyl phenates is contemplated, varying in the alkyl radical and varying in the content of ethe noxy units, so long as they are water-dispersible.

I claim:

1. Non-ionic water-dispersible material comprising all the non-aqueous content of the reaction mass resulting from the condensation reaction of alkyl phenol and ethylene oxide and further comprising essentially a major portion of polyethenoxy ethers of alkyl phenol and a minor portion of the reaction products of an aqueous solution of hydrogen peroxide and fluorescent contaiminants of said ethers produced in side reactions attending formation of said ethers.

2. A mixture comprising all the non-aqueous content of the condensation reaction of alkyl phenol and ethylene oxide, and containing water-dispersible polyethenoxy ethers of alkyl phenol formed from ethylene oxide and alkyl phenol and relative to the amount of said ethers a minor proportion of non-fluorescent material, said latter being the product of oxidizing with an aqueous solution of hydrogen peroxide fluorescent substance produced in side reactions attending the said formation of said ethers from alkyl phenol and ethylene oxide.

3. A substantially non-fluorescent mixture comprising all the non-aqueous content of the condensation reaction of alkyl phenol and ethylene oxide, and containing waterdispersible polyethenoxy ethers of alkyl phenol formed from ethylene oxide and alkyl phenol and relative to the amount of said ethers a minor proportion of nonfluorescent material, said latter being the product of oxidizing with an aqueous solution of hydrogen peroxide fluorescent substance produced in side reactions attending the said formation of said ethers from alkyl phenol and ethylene oxide.

4. The method of removing fluorescent colored impurities from a water-dispersible ether mass resulting from condensing alkyl phenol with ethylene oxide, which comprises subjecting the said mass to the action of an aqueous solution of hydrogen peroxide in quantity sufficient at least to increase the light-transmittancy of the resulting mass.

5. The method of removing fluorescent colored impurities from a water-dispersible ether mass resulting from condensing alkyl phenol with ethylene oxide, which comprises subjecting said mass to the action of an aqueous solution of hydrogen peroxide in quantity to increase the light-transmittancy of the resulting mass substantially to a maximum whereby the fluorescent content is removed.

6. Non-ionic water-dispersible material comprising all the non-aqueous content of the reaction mass resulting from the condensation reaction of ethylene oxide and phenol selected from the group consisting of octyl and nonyl phenol, and further comprising essentially a major 6 portion of polyethenoxy ethers of said selected phenol and a minor portion of the non-fluorescent reaction products of an aqueous solution of hydrogen peroxide and fluorescent contaminants of said ethers produced in side reactions attending formation of said ethers.

7. Non-ionic water-dispersible material comprising all the nonaqueous content of the reaction mass resulting from the condensation reaction of ethylene oxide and phenol selected from the group consisting of octyl phenol and nonyl phenol, and further comprising essentially a major portion of polyethenoxy ethers of said selected phenol and a minor portion of the non-fluorescent reaction products of an aqueous solution of hydrogen peroxide and fluorescent contaminants of said ethers produced in side reactions attending formation of said ethers, said contaminants being colored and fluorescent and subject to loss of fluorescence and to lightening of color by reaction with hydrogen peroxide.

8. Substantially non-fluorescent non-ionic water-dispersible material comprising all the non-aqueous content of the reaction mass resulting from the condensation reaction of ethylene oxide and phenol selected from the group consisting of octyl phenol and nonyl phenol, and further comprising essentially a major portion of polyethenoxy ethers of said selected phenol and a minor portion of the non-fluorescent reaction products of an aqueous solution of hydrogen peroxide and fluorescent contaminants of said ethers produced in side reactions attending formation of said ethers.

9. The method of lessening the content of fluorescent colored impurities from a water-dispersible ether mass resulting from condensing ethylene oxide with a phenol selected from the group consisting of octyl phenol and nonyl phenol, which comprises subjecting the said mass to the action of aqueous hydrogen peroxide in quantity sutficient at least to increase the light-transmittancy and to lessen the fluorescence of the resulting mass.

10. The method of removing fluorescent colored impurities from a water-dispersible ether mass resulting from condensing ethylene oxide with a phenol selected from the group consisting of octyl phenol and nonyl phenol, which comprises subjecting the said mass to the action of aqueous hydrogen peroxide in quantity sufficient to increase the light-transmittancy of the resulting mass substantially to a maximum value available thereby and to render the resulting mass substantially non-fluorescent.

References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoeller et al Aug. 21, 1934 2,075,018 Bruson et al. Mar. 30, 1937 2,496,582 Enyeart Feb. 7, 1950 2,555,285 Black May 29, 1951 2,723,294 Benoit Nov. 8, 1955 

2. A MIXTURE COMPRISING ALL THE NON-AQUEOUS CONTENT OF THE CONDENSATION REACTION OF ALKYL PHENOL AND ETHYLENE OXIDE, AND CONTAINING WATER-DISPERSIBLE POLYETHENOXY ETHERS OF ALKYL PHENOL FORMED FROM ETHYLENE OXIDE AND ALKYL PHENOL AND RELATIVE TO THE AMOUNT OF SAID ETHERS A MINOR PROPORTION OF NON-FLUORESCENT MATERIAL, SAID LATTER BEING THE PRODUCT OF OXIDIZING WITH AN AQUEOUS SOLUTION OF HYDROGEN PEROXIDE FLUORESCENT SUBSTANCE PRODUCED IN SIDE REACTIONS ATTENDING THE SAID FORMATION OF SAID ETHERS FROM ALKYL PHENOL AND ETHYLENE OXIDE. 